CN107573452B - A kind of copolymerization REPVDC alloy emulsion and its preparation method and application - Google Patents
A kind of copolymerization REPVDC alloy emulsion and its preparation method and application Download PDFInfo
- Publication number
- CN107573452B CN107573452B CN201710935664.0A CN201710935664A CN107573452B CN 107573452 B CN107573452 B CN 107573452B CN 201710935664 A CN201710935664 A CN 201710935664A CN 107573452 B CN107573452 B CN 107573452B
- Authority
- CN
- China
- Prior art keywords
- copolymerization
- monomer
- initiator
- repvdc
- alloy emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to a kind of copolymerization REPVDC alloy emulsions and its preparation method and application, including seed emulsion.Applied to steel structure aqueous heavy antisepsis, food packaging or birds, beasts and eggs, preserving fruit and vegetable utilizing.The present invention is copolymerized by the way that function monomer and vinylidene chloride is added, it can change the crystalline texture of PVDC side chain distortion, become the crystallizable side chain structure of ordered arrangement, to which the intensity, toughness and barrier property of former PVDC be significantly increased, 0.3-3 times of mechanical property raising, heat resistance improve 20-60% and have been assigned Memorability new material on the basis of the original；Preparation process is simple, at low cost, has a good application prospect.
Description
Technical field
The invention belongs to polymeric material field, in particular to a kind of copolymerization REPVDC alloy emulsion and preparation method thereof and
Using.
Background technique
A kind of polyvinylidene chloride (abbreviation PVDC) the high molecular material packaging material good as materials with high barrier property, safety
It is nontoxic, it has a wide range of applications in food packaging applications.But PVDC is often exactly thermal stability ratio as packaging material at present
Poor, thermal decomposition temperature is at 100-120 DEG C, when the heated or room temperature time is longer, will generate double bond conjugation, escape chlorine
Change hydrogen, makes intermolecular generation cavity, barrier property failure, when leading to that the additives increase such as addition preservative is also needed to save in food
Between, certain harm is often had to human body.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of copolymerization REPVDC alloy emulsion and preparation method thereof and answer
With the alloy emulsion is copolymerized by the way that function monomer and vinylidene chloride is added, thus it is possible to vary the crystalline texture of PVDC side chain distortion,
Become the crystallizable side chain structure of ordered arrangement, so that the intensity, toughness and barrier property of former PVDC be significantly increased, new material exists
0.3-3 times of mechanical property raising, heat resistance improve 20-60% and have been assigned Memorability on the basis of originally；Preparation process
Simply, at low cost, it has a good application prospect.
A kind of copolymerization REPVDC alloy emulsion of the invention, by mass percentage, including following components:
The rare earth/metallic compound function monomer raw material composition includes mother liquor, alicyclic organic, auxiliary agent and deionized water；
Wherein, mother liquor includes rare earth compound or metallic compound, organic acid, organic amine and deionized water.
Further, the rare earth compound or metallic compound are oxide, hydroxide or the salt of rare earth or metal
One or more of.Wherein, the preferred low oxide of oxide, the preferred carbonate of salt.
Further, the rare earth is lanthanum, cerium, europium, terbium or neodymium element；The metal be zinc, calcium, magnesium, manganese, copper, nickel,
Aluminium, niobium, molybdenum, ruthenium, tungsten, rhenium or hafnium element.
Further, the organic acid is citric acid, in maleic acid, ethylenediamine tetra-acetic acid, succinic acid, adipic acid
It is one or more of.
Further, the organic amine is one of diethylamine, ethylenediamine, allyl amine, diethylenetriamines or several
Kind.
Preferably, the mother liquor is by mass percentage, comprising: rare earth compound or metallic compound 6-9%, organic acid
15%-25%, organic amine 10-20%, surplus are deionized water.
Further, the alicyclic organic is acrylate or epoxy-ester.
Further, the acrylate is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, maleic acid
One or more of fourth diester；The epoxy-ester is one or both of epoxy aliphatic acid methyl ester, epoxy acrylate.
Further, the auxiliary agent includes catalyst and polymerization inhibitor, and the mass ratio of catalyst and polymerization inhibitor is 1:2-5.
Further, the catalyst is p-methyl benzenesulfonic acid；The polymerization inhibitor is hydroquinone, methylnaphthohydroquinone THQ, right
One or more of hydroxyanisol HQMME, p methoxy phenol MEHQ.
Preferably, the raw material forms by mass percentage, including mother liquor 18-28%, alicyclic organic 48-58%, auxiliary agent 0.1
~2%, surplus is deionized water.
Further, the composition of the mix monomer emulsifier includes emulsifier, wetting agent, protective glue and deionized water.
Preferably, mix monomer emulsifier is by mass percentage (on the basis of alloy emulsion total amount), comprising:
Further, the composition of the bottom material include seed emulsion, emulsifier, wetting agent, protective glue, pH adjusting agent and
Deionized water.
Preferably, bottom material is by mass percentage (on the basis of alloy emulsion total amount), comprising:
Preferably, the emulsifier is non-ionic fatty acid polyglycol ethylene oxide ether.
Preferably, the wetting agent is anionic fluorochemical surfactant or siliceous anionic surfactant.
Preferably, the protective glue is Phosphate Anionic Surfactants or sulfonate anionic surfactant.
Preferably, the pH adjusting agent is one of ammonium hydrogen carbonate, glacial acetic acid, diammonium hydrogen phosphate, potassium dihydrogen phosphate
Or it is several.
The seed emulsion by mass percentage, including following components:
Preferably, the initiator includes initiator A and initiator B；Wherein, initiator A includes oxidant and deionization
Water；Initiator B includes reducing agent and deionized water.
Preferably, the oxidant is one or more of hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate.
Preferably, the reducing agent is one or more of rongalite, sodium hydrogensulfite, hydrogen phosphite sodium.
Further, the additive amount of the stabilizer is the 4-6 ‰ of lotion gross mass.
The stabilizer is by mass percentage (on the basis of alloy emulsion total amount), comprising:
Antioxidant 0.1-0.5 ‰；
Anti-aging agent 0.3-0.6 ‰；
Vinylidene chloride 4-5 ‰.
Preferably, the antioxidant is one or more of BHT, 1010, TPP.
Preferably, the anti-aging agent is one or more of UV-531, UV-9, UV-P, antioxidant H, antioxidant MB.
The present invention also provides a kind of preparation methods for being copolymerized REPVDC alloy emulsion, comprising:
(1) monomer is mixed in proportion, keeps the temperature 30min-60min in 17 ± 2.5 DEG C of addition mix monomer emulsifiers, obtains
Pre-emulsified mix monomer；
(2) bottom material is added in polymeric kettle, vacuumizes stirring, set temperature is 50-55 DEG C, when temperature is raised to 34-42
DEG C when, start to be added dropwise to emulsification mix monomer and initiator, calculate monomer dropping amount/5 minute, drip off within 13-14 hours, work as monomer
After dripping off, 1 hour is kept the temperature, starts that regulator is added dropwise, calculates regulator dripping quantity/5 minute, drip off within 20-30 minutes；It calculates and causes
Dripping quantity/5 minute of agent drip off for 17-18 hours, after initiator drips off, keep the temperature 1-2h after, logical nitrogen take off it is 2-3 hour dilute after, drop
When temperature arrives≤35 DEG C, copolymerization REPVDC alloy emulsion is obtained by filtration in discharging.
The present invention also provides a kind of application for being copolymerized REPVDC alloy emulsion, the alloy emulsion is applied to steel structure water
Property heavy antisepsis, food packaging or birds, beasts and eggs, preserving fruit and vegetable utilizing.
The alloy emulsion of rare earth/metallic compound and vinylidene chloride of the present invention, the alloy emulsion performance are better than gathering inclined two
The performance of vinyl chloride PVDC, specific as follows:
(1) by the thermal stability factor of PVDC by 100-110 DEG C, 150 DEG C are increased to greater than, 140 DEG C of the fusing point greater than PVDC；
Solve the problems, such as that existing pure PVDC resin is unable to blown film, injection molding.
(2) crystalline texture that PVDC side chain can be distorted after rare earth, metal ion is added, is changed to the side chain of ordered arrangement
Crystalline texture, so that the intensity, toughness and barrier property of PVDC be greatly improved.
(3) preservative film, food flexible packing, fermented liquid food packaging bottle, the medicine bottle, cosmetics of pure PVDC resin are realized
The industrialization of bottle etc., reduces or prevents the use of food preservative.
Since rare earth element is abbreviated as " RE " in English, " RE " has the meaning traced back, remanufactured again, institute again in English
Rare earth/metal alloy PVDC of this copolymerization is named as REPVDC with the difference in order to distinguish existing PVDC material.
Beneficial effect
The present invention is copolymerized by the way that function monomer and vinylidene chloride is added, thus it is possible to vary the crystallization knot of PVDC side chain distortion
Structure, becomes the crystallizable side chain structure of ordered arrangement, so that the intensity, toughness and barrier property of former PVDC, green wood be significantly increased
0.3-3 times of mechanical property raising, heat resistance improve 20-60% and have been assigned Memorability material on the basis of the original；Preparation
Simple process and low cost has a good application prospect.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The formula of function monomer in embodiment is as follows:
Mother liquor formula is as follows:
| Title | Deionized water | Citric acid | Lanthanum carbonate | Diethylamine |
| Mass percent | 61.20% | 21.70% | 6.30% | 10.80% |
Function monomer formula is as follows:
| Title | Deionized water | Mother liquor | P-methyl benzenesulfonic acid | Hydroquinone | Ethyl acrylate |
| Mass percent | 25.20% | 24.60% | 0.20% | 0.68% | 49.32% |
This formula is only for example, function monomer required for can preparing according to actual demand in practical operation.
Embodiment 1
The formula of the seed emulsion of copolymerization REPVDC alloy emulsion provided in this embodiment is as follows:
Mix monomer
Mix monomer emulsifier
Bottom material
Initiator
The preparation method is as follows:
(1) mix monomer is pressed into formula rate, poured into mix monomer kettle, and be stirred continuously.
(2) it is formulated into monomer emulsifying kettle, after sealing, is vacuumized, nitrogen charging in mix monomer emulsifiers formula ratio
Gas three times, then inflated with nitrogen, so that pressure gauge is zeroed, and be stirred continuously, temperature is controlled at 17 ± 2.5 DEG C.
(3) metering pump is opened, mix monomer was added drop-wise in monomer emulsifying kettle at 90 minutes or so, then 17 ± 2.5 DEG C of guarantors
After temperature stirring 30 minutes, emulsified monomer is obtained, that is, can be used.
(4) bottom material is pressed into formula rate, is formulated into polymeric kettle, after sealing, vacuumize, inflated with nitrogen three times, take out again true
Sky guarantee pressure is stirred continuously between -0.09--0.080, and revolving speed is 600-800 revs/min, set temperature 60
℃。
(5) starting that initiator is added dropwise when temperature is raised to 48 DEG C, dripping quantity is (initiator total amount) 4.5-5 ‰/5 minute,
It drips off within 17 hours.
(6) start the emulsified monomer in a dropping step (3) when temperature is raised to 52 DEG C, dripping quantity is (emulsified monomer total amount)
It 5.8-6.2 ‰/5 minute, drips off within 14 hours.
After (7) 60 DEG C keep the temperature 3 hours, adjustment temperature setting is 55 DEG C, until monomer drips off.
(8) 1 hour is kept the temperature after monomer drips off, adjustment temperature setting is 52 DEG C, until initiator drips off.
(9) after initiator drips off, after heat preservation 1 hour, start to cool down.
(10) it when 35 DEG C of temperature <, opens simultaneously polymeric kettle bottom and takes off dilute (take off dilute be meant that and remove unreacted monomer)
Nitrogen valve and vacuum pump switch, start to take off it is dilute, after 2 hours, from the concentration of sample cock sampling analysis residual monomer, until
Until complying with standard, turns off and take off dilute valve and vacuum pump.
(11) gas valve is opened, is made after pressure is equal with atmosphere in polymeric kettle, is discharged.
The seed emulsion film clarity of the present embodiment is high, lotion filtering residue is more, storage stability is good；Preparation process is poly-
Resultant pressure is high, is easily demulsified.
Embodiment 2
The formula of the seed emulsion of copolymerization REPVDC alloy emulsion provided in this embodiment is as follows:
Mix monomer
Mix monomer emulsifier
Bottom material
Initiator
The preparation method is as follows:
(1) mix monomer is pressed into formula rate, poured into mix monomer kettle, and be stirred continuously.
(2) it is formulated into monomer emulsifying kettle, after sealing, is vacuumized, nitrogen charging in mix monomer emulsifiers formula ratio
Gas three times, then inflated with nitrogen, so that pressure gauge is zeroed, and be stirred continuously, temperature is controlled at 17 ± 2.5 DEG C.
(3) metering pump is opened, mix monomer was added drop-wise in monomer emulsifying kettle at 90 minutes or so, then 17 ± 2.5 DEG C of guarantors
After temperature stirring 30 minutes, emulsified monomer is obtained, that is, can be used.
(4) bottom material is pressed into formula rate, is formulated into polymeric kettle, after sealing, vacuumize, inflated with nitrogen three times, take out again true
Sky guarantee pressure is stirred continuously between -0.09--0.080, and revolving speed is 600-800 revs/min, set temperature 55
℃。
(5) starting that initiator is added dropwise when temperature is raised to 43 DEG C, dripping quantity is (initiator total amount) 4.5-5 ‰/5 minute,
It drips off within 17 hours.
(6) start the emulsified monomer in a dropping step (3) when temperature is raised to 48 DEG C, dripping quantity is (emulsified monomer total amount)
It 5.8-6.2 ‰/5 minute, drips off within 14 hours.
After (7) 55 DEG C keep the temperature 3 hours, adjustment temperature setting is 52 DEG C, until monomer drips off.
(8) 1 hour is kept the temperature after monomer drips off, adjustment temperature setting is 50 DEG C, until initiator drips off.
(9) after initiator drips off, after heat preservation 1 hour, start to cool down.
(10) it when 35 DEG C of temperature <, opens simultaneously polymeric kettle bottom and takes off dilute nitrogen valve and vacuum pump switch, start
It takes off dilute, after 2 hours, from the concentration of sample cock sampling analysis residual monomer, until complying with standard, turns off and take off dilute valve
And vacuum pump.
(11) gas valve is opened, is made after pressure is equal with atmosphere in polymeric kettle, is discharged.
The seed emulsion of the present embodiment forms a film good barrier property (the salt spray test time is long), filtering residue is few, stable storage one
As；It is few that preparation process polymerization pressure is moderate, the lotion rate of recovery is up to 99.3%, residual monomer.
Embodiment 3
The formula of the seed emulsion of copolymerization REPVDC alloy emulsion provided in this embodiment is as follows:
Mix monomer
Mix monomer emulsifier
Bottom material
Initiator
The preparation method is as follows:
(1) mix monomer is pressed into formula rate, poured into mix monomer kettle, and be stirred continuously.
(2) it is formulated into monomer emulsifying kettle, after sealing, is vacuumized, nitrogen charging in mix monomer emulsifiers formula ratio
Gas three times, then inflated with nitrogen, so that pressure gauge is zeroed, and be stirred continuously, temperature is controlled at 17 ± 2.5 DEG C.
(3) metering pump is opened, mix monomer was added drop-wise in monomer emulsifying kettle at 90 minutes or so, then 17 ± 2.5 DEG C of guarantors
After temperature stirring 30 minutes, emulsified monomer is obtained, that is, can be used.
(4) bottom material is pressed into formula rate, is formulated into polymeric kettle, after sealing, vacuumize, inflated with nitrogen three times, take out again true
Sky guarantee pressure is stirred continuously between -0.09--0.080, and revolving speed is 600-800 revs/min, set temperature 55
℃。
(5) starting that initiator is added dropwise when temperature is raised to 48 DEG C, dripping quantity is (initiator total amount) 4.5-5 ‰/5 minute,
It drips off within 17 hours.
(6) start the emulsified monomer in a dropping step (3) when temperature is raised to 52 DEG C, dripping quantity is (emulsified monomer total amount)
It 5.8-6.2 ‰/5 minute, drips off within 14 hours.
After (7) 55 DEG C keep the temperature 3 hours, adjustment temperature setting is 50 DEG C, until monomer drips off.
(8) 1 hour is kept the temperature after monomer drips off, adjustment temperature setting is 48 DEG C, until initiator drips off.
(9) after initiator drips off, after heat preservation 1 hour, start to cool down.
(10) it when 35 DEG C of temperature <, opens simultaneously polymeric kettle bottom and takes off dilute nitrogen valve and vacuum pump switch, start
It takes off dilute, after 2 hours, from the concentration of sample cock sampling analysis residual monomer, until complying with standard, turns off and take off dilute valve
And vacuum pump.
(11) gas valve is opened, is made after pressure is equal with atmosphere in polymeric kettle, is discharged.
The seed emulsion film forming adhesive force of the present embodiment is good, barrier property is more slightly lower than embodiment 2, lotion filtering is without slag, storage
Stability is general；Preparation process polymerization pressure is moderate, the lotion rate of recovery is high, residual monomer is more slightly higher than embodiment 2.
Embodiment 4
The formula of copolymerization REPVDC alloy emulsion provided in this embodiment is as follows:
Mix monomer
Mix monomer emulsifier
Bottom material
Initiator
Stabilizer:
The preparation method is as follows:
(1) mix monomer is pressed into formula rate, poured into mix monomer kettle, and be stirred continuously.
(2) it is formulated into monomer emulsifying kettle, after sealing, is vacuumized, nitrogen charging in mix monomer emulsifiers formula ratio
Gas three times, then inflated with nitrogen, so that pressure gauge is zeroed, and be stirred continuously, temperature is controlled at 17 ± 2.5 DEG C.
(3) metering pump is opened, mix monomer was added drop-wise in monomer emulsifying kettle at 90 minutes or so, then 17 ± 2.5 DEG C of guarantors
After temperature stirring 30 minutes, emulsified monomer is obtained, that is, can be used.
(4) bottom material is pressed into formula rate, is formulated into polymeric kettle, after sealing, vacuumize, inflated with nitrogen three times, take out again true
Sky guarantee pressure is stirred continuously between -0.09--0.080, and revolving speed is 600-800 revs/min, set temperature 52
℃。
(5) starting that initiator is added dropwise when temperature is raised to 38 DEG C, dripping quantity is (initiator total amount) 4.5-5 ‰/5 minute,
It drips off within 17 hours.
(6) start the emulsified monomer in a dropping step (3) when temperature is raised to 42 DEG C, dripping quantity is (emulsified monomer total amount)
It 5.8-6.2 ‰/5 minute, drips off within 14 hours.
(7) 52 DEG C are kept, until monomer drips off.
(8) 1 hour is kept the temperature after monomer drips off, adjustment temperature setting is 50 DEG C.
(9) when temperature is equal to 50 DEG C, starting that regulator is added dropwise, dripping quantity is (regulator total amount) 15-17%/5 minute,
It drips off within 25-35 minutes.
(10) after initiator drips off, after heat preservation 1 hour, start to cool down.
(11) it when 35 DEG C of temperature <, opens simultaneously polymeric kettle bottom and takes off dilute nitrogen valve and vacuum pump switch, start
It takes off dilute, after 2 hours, from the concentration of sample cock sampling analysis residual monomer, until complying with standard, turns off and take off dilute valve
And vacuum pump.
(12) gas valve is opened, is made after pressure is equal with atmosphere in polymeric kettle, is discharged.
The emulsion film forming adhesive force of the present embodiment is good；Preparation process polymerization pressure is moderate, good emulsion stability, emulsion particle diameter
Range is wide, lotion has micro residual monomer, and it is short to take off dilute time.
Embodiment 5
The formula of copolymerization REPVDC alloy emulsion provided in this embodiment is as follows:
Mix monomer
Mix monomer emulsifier
Bottom material
Initiator
Stabilizer:
The preparation method is as follows:
(1) mix monomer is pressed into formula rate, poured into mix monomer kettle, and be stirred continuously.
(2) it is formulated into monomer emulsifying kettle, after sealing, is vacuumized, nitrogen charging in mix monomer emulsifiers formula ratio
Gas three times, then inflated with nitrogen, so that pressure gauge is zeroed, and be stirred continuously, temperature is controlled at 17 ± 2.5 DEG C.
(3) metering pump is opened, mix monomer was added drop-wise in monomer emulsifying kettle at 90 minutes or so, then 17 ± 2.5 DEG C of guarantors
After temperature stirring 30 minutes, emulsified monomer is obtained, that is, can be used.
(4) bottom material is pressed into formula rate, is formulated into polymeric kettle, after sealing, vacuumize, inflated with nitrogen three times, take out again true
Sky guarantee pressure is stirred continuously between -0.09--0.080, and revolving speed is 600-800 revs/min, set temperature 50
℃。
(5) starting that initiator is added dropwise when temperature is raised to 36 DEG C, dripping quantity is (initiator total amount) 4.5-5 ‰/5 minute,
It drips off within 17 hours.
(6) start the emulsified monomer in a dropping step (3) when temperature is raised to 44 DEG C, dripping quantity is (emulsified monomer total amount)
It 5.8-6.2 ‰/5 minute, drips off within 14 hours.
(7) 50 DEG C are kept, until monomer drips off.
(8) 1 hour is kept the temperature after monomer drips off, adjustment temperature setting is 48 DEG C.
(9) when temperature is equal to 48 DEG C, starting that regulator is added dropwise, dripping quantity is (regulator total amount) 15-17%/5 minute,
It drips off within 25-35 minutes.
(10) after initiator drips off, after heat preservation 1 hour, start to cool down.
(11) it when 35 DEG C of temperature <, opens simultaneously polymeric kettle bottom and takes off dilute nitrogen valve and vacuum pump switch, start
It takes off dilute, after 2 hours, from the concentration of sample cock sampling analysis residual monomer, until complying with standard, turns off and take off dilute valve
And vacuum pump.
(12) gas valve is opened, is made after pressure is equal with atmosphere in polymeric kettle, is discharged.
The emulsion film forming good barrier property of the present embodiment；Preparation process polymerization pressure is moderate, good emulsion stability, emulsion particle diameter
Moderate range, residual monomer is few, and it is moderate to take off dilute time.
Embodiment 6
The formula of copolymerization REPVDC alloy emulsion provided in this embodiment is as follows:
Mix monomer
Mix monomer emulsifier
Bottom material
Initiator
Stabilizer:
The preparation method is as follows:
(1) mix monomer is pressed into formula rate, poured into mix monomer kettle, and be stirred continuously.
(2) it is formulated into monomer emulsifying kettle, after sealing, is vacuumized, nitrogen charging in mix monomer emulsifiers formula ratio
Gas three times, then inflated with nitrogen, so that pressure gauge is zeroed, and be stirred continuously, temperature is controlled at 17 ± 2.5 DEG C.
(3) metering pump is opened, mix monomer was added drop-wise in monomer emulsifying kettle at 90 minutes or so, then 17 ± 2.5 DEG C of guarantors
After temperature stirring 30 minutes, emulsified monomer is obtained, that is, can be used.
(4) bottom material is pressed into formula rate, is formulated into polymeric kettle, after sealing, vacuumize, inflated with nitrogen three times, take out again true
Sky guarantee pressure is stirred continuously between -0.09--0.080, and revolving speed is 600-800 revs/min, set temperature 48
℃。
(5) starting that initiator is added dropwise when temperature is raised to 34 DEG C, dripping quantity is (initiator total amount) 4.5-5 ‰/5 minute,
It drips off within 17 hours.
(6) start the emulsified monomer in a dropping step (3) when temperature is raised to 34 DEG C, dripping quantity is (emulsified monomer total amount)
5.8-6.2 ‰/5 minute, dripping off within 14 hours.
(7) 48 DEG C are kept, until monomer drips off.
(8) 1 hour is kept the temperature after monomer drips off, adjustment temperature setting is 45 DEG C.
(9) when temperature is equal to 45 DEG C, starting that regulator is added dropwise, dripping quantity is (regulator total amount) 15-17%/5 minute,
It drips off within 25-35 minutes.
(10) after initiator drips off, after heat preservation 1 hour, start to cool down.
(11) it when 35 DEG C of temperature <, opens simultaneously polymeric kettle bottom and takes off dilute nitrogen valve and vacuum pump switch, start
It takes off dilute, after 2 hours, from the concentration of sample cock sampling analysis residual monomer, until complying with standard, turns off and take off dilute valve
And vacuum pump.
(12) gas valve is opened, is made after pressure is equal with atmosphere in polymeric kettle, is discharged.
The emulsion film forming good ultraviolet resistance of the present embodiment；Preparation process polymerization pressure is moderate, good emulsion stability, lotion grain
Diameter narrow range, residual monomer is little higher, and it is slightly long to take off dilute time.
Test result is as follows for the emulsion property of embodiment 4~6:
Embodiment 1,2,3 is seed emulsion, only when alloy emulsion polymerize, is added in bottom material and does seed use, remaining does not have
There is utility value；The difference of three kinds of seed emulsions is that molecular size range is different, physical relationship are as follows: 1 <, 2 < 3；It is closed in polymerization
When golden lotion, different seed emulsions can be selected according to the difference of required molecular weight.
Claims (15)
1. a kind of copolymerization REPVDC alloy emulsion, it is characterised in that: by mass percentage, including following components:
The rare earth/metallic compound function monomer raw material composition includes mother liquor, organic ester, auxiliary agent and deionized water；Wherein,
Mother liquor is by mass percentage, comprising: rare earth compound or metallic compound 6-9%, organic acid 15%-25%, organic amine 10-
20%, surplus is deionized water；The organic ester is acrylate；The auxiliary agent includes catalyst and polymerization inhibitor；
The rare earth is lanthanum, cerium, europium, terbium or neodymium element；The metal be zinc, calcium, magnesium, manganese, copper, nickel, aluminium, niobium, molybdenum, ruthenium, tungsten,
Rhenium or hafnium element；
The organic acid is one or more of citric acid, maleic acid, ethylenediamine tetra-acetic acid, succinic acid, adipic acid；
The organic amine is one or more of diethylamine, ethylenediamine, allyl amine, diethylenetriamines；
The acrylate is one or more of ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer；
The catalyst is p-methyl benzenesulfonic acid；The polymerization inhibitor is hydroquinone, methylnaphthohydroquinone THQ, p-hydroxyanisole
One or more of HQMME, p methoxy phenol MEHQ.
2. a kind of copolymerization REPVDC alloy emulsion according to claim 1, it is characterised in that: the rare earth compound or gold
Belonging to compound is one or more of rare earth or oxide, hydroxide or the carbonate of metal.
3. a kind of copolymerization REPVDC alloy emulsion according to claim 1, it is characterised in that: the rare earth/metal compound
The raw material of object function monomer forms by mass percentage, including mother liquor 18-28%, organic ester 48-58%, auxiliary agent 0.1~2%,
Surplus is deionized water.
4. a kind of copolymerization REPVDC alloy emulsion according to claim 1, it is characterised in that: the mix monomer emulsifier
Composition include emulsifier, wetting agent, protective glue and deionized water.
5. a kind of copolymerization REPVDC alloy emulsion according to claim 4, it is characterised in that: the mix monomer emulsifier
By mass percentage, comprising:
6. a kind of copolymerization REPVDC alloy emulsion according to claim 1, it is characterised in that: the composition of the bottom material includes
Seed emulsion, emulsifier, wetting agent, protective glue, pH adjusting agent and deionized water.
7. a kind of copolymerization REPVDC alloy emulsion according to claim 6, it is characterised in that: the bottom material presses quality percentage
Than, comprising:
8. according to a kind of any copolymerization REPVDC alloy emulsion of claim 4-7, it is characterised in that: the emulsifier is
Non-ionic fatty acid polyglycol ethylene oxide ether；The wetting agent is that anionic fluorochemical surfactant or siliceous anionic surface are living
Property agent；The protective glue is Phosphate Anionic Surfactants or sulfonate anionic surfactant.
9. a kind of copolymerization REPVDC alloy emulsion according to claim 1, it is characterised in that: the seed emulsion presses quality
Percentage, including following components:
10. a kind of copolymerization REPVDC alloy emulsion according to claim 9, it is characterised in that: the initiator includes drawing
Send out agent A and initiator B；Wherein, initiator A includes oxidant and deionized water；Initiator B includes reducing agent and deionized water.
11. a kind of copolymerization REPVDC alloy emulsion according to claim 10, it is characterised in that: the oxidant is dioxygen
One or more of water, ammonium persulfate, potassium peroxydisulfate；The reducing agent is rongalite, in sodium hydrogensulfite, hydrogen phosphite sodium
One or more.
12. a kind of copolymerization REPVDC alloy emulsion according to claim 1, it is characterised in that: the stabilizer presses quality
Percentage, comprising:
Antioxidant 0.1-0.5 ‰；
Anti-aging agent 0.3-0.6 ‰；
Vinylidene chloride 4-5 ‰.
13. a kind of copolymerization REPVDC alloy emulsion according to claim 12, it is characterised in that: the antioxidant be BHT,
1010, one or more of TPP；The anti-aging agent is one of UV-531, UV-9, UV-P, antioxidant H, antioxidant MB
Or it is several.
14. a kind of preparation method of copolymerization REPVDC alloy emulsion as described in claim 1, comprising:
(1) monomer is mixed in proportion, keeps the temperature 30min-60min in 17 ± 2.5 DEG C of addition mix monomer emulsifiers, obtains pre- cream
The mix monomer of change；
(2) bottom material being added in polymeric kettle, vacuumizes stirring, set temperature is 50-55 DEG C, when temperature is raised to 34-42 DEG C,
Start to be added dropwise to emulsification mix monomer and initiator, calculates monomer dropping amount/5 minute, drip off within 13-14 hours, when monomer drips off
Afterwards, 1 hour is kept the temperature, starts that regulator is added dropwise, calculates regulator dripping quantity/5 minute, drip off within 20-30 minutes；Calculate initiator
Dripping quantity/5 minute drip off for 17-18 hours, after initiator drips off, keep the temperature 1-2h after, logical nitrogen take off it is 2-3 hours dilute after, cool to
At≤35 DEG C, copolymerization REPVDC alloy emulsion is obtained by filtration in discharging.
15. a kind of application of copolymerization REPVDC alloy emulsion as described in claim 1, it is characterised in that: the alloy emulsion
Applied to steel structure aqueous heavy antisepsis, food packaging or birds, beasts and eggs, preserving fruit and vegetable utilizing.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710935664.0A CN107573452B (en) | 2017-10-10 | 2017-10-10 | A kind of copolymerization REPVDC alloy emulsion and its preparation method and application |
| JP2020539123A JP2020536163A (en) | 2017-10-10 | 2018-03-23 | Rare earth / metal compound functional monomer and its manufacturing method, application |
| EP18867107.7A EP3677601B1 (en) | 2017-10-10 | 2018-03-23 | Rare earth/metal compound functional monomer and preparation method therefor and application thereof |
| PCT/CN2018/080192 WO2019071920A1 (en) | 2017-10-10 | 2018-03-23 | Rare earth/metal compound functional monomer and preparation method therefor and application thereof |
| US16/845,039 US11472941B2 (en) | 2017-10-10 | 2020-04-09 | Functional monomer comprising rare earth/metal compound, preparation method thereof, and method of using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710935664.0A CN107573452B (en) | 2017-10-10 | 2017-10-10 | A kind of copolymerization REPVDC alloy emulsion and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107573452A CN107573452A (en) | 2018-01-12 |
| CN107573452B true CN107573452B (en) | 2019-10-29 |
Family
ID=61040425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710935664.0A Active CN107573452B (en) | 2017-10-10 | 2017-10-10 | A kind of copolymerization REPVDC alloy emulsion and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107573452B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3677601B1 (en) * | 2017-10-10 | 2023-06-21 | Shanghai Lufeng Auxiliary Co., Ltd | Rare earth/metal compound functional monomer and preparation method therefor and application thereof |
| CN108410280B (en) * | 2018-03-02 | 2020-11-13 | 浙江衢州巨塑化工有限公司 | Preparation method of PVDC aqueous emulsion for coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649015A (en) * | 2009-08-27 | 2010-02-17 | 浙江野风塑胶有限公司 | Polyvinylidene chloride (PVDC) copolymer latex for medicine packaging as well as preparation method and application thereof |
| CN104028312A (en) * | 2013-12-20 | 2014-09-10 | 江苏佳华新材料科技有限公司 | A preparing method of a rare earth catalytic cracking double-metal deactivator |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3974882B2 (en) * | 2003-08-07 | 2007-09-12 | 信越化学工業株式会社 | Polymer scale adhesion inhibitor |
| CN103193918A (en) * | 2013-05-06 | 2013-07-10 | 南通瑞普埃尔生物工程有限公司 | Vinyl chloride-vinylidene chloride (VDC)/acrylic acid (AA)/methyl methacrylate (MMA)/acrylonitrile (AN) copolymerized polyvinyl dichloride (PVDC) emulsion and preparation method thereof |
-
2017
- 2017-10-10 CN CN201710935664.0A patent/CN107573452B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649015A (en) * | 2009-08-27 | 2010-02-17 | 浙江野风塑胶有限公司 | Polyvinylidene chloride (PVDC) copolymer latex for medicine packaging as well as preparation method and application thereof |
| CN104028312A (en) * | 2013-12-20 | 2014-09-10 | 江苏佳华新材料科技有限公司 | A preparing method of a rare earth catalytic cracking double-metal deactivator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107573452A (en) | 2018-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2025688B1 (en) | Polyvinyl ester dispersions, method for their manufacture and application thereof | |
| CN107573452B (en) | A kind of copolymerization REPVDC alloy emulsion and its preparation method and application | |
| EP3080225B1 (en) | Aqueous adhesive composition | |
| CN106279493B (en) | A kind of high viscosity high solids content vinyl acetate-ethylene copolymerization emulsions and its production method | |
| CN105085778A (en) | Coating material composition aqueous latex for slowly releasing function components, preparation method and applications thereof | |
| CN108219054A (en) | A kind of preparation method of vinyl acetate-ethylene copolymerization emulsions | |
| CN109134736A (en) | A kind of anticorrosive paint aqueous polyvinylidene dichloroethylene-acrylic ester copolymer latex and preparation method thereof | |
| EP0699692B1 (en) | Aqueous dispersions for adhesives | |
| CN106189960B (en) | A kind of water base Emulsion for bi-component wood bonding adhesive and preparation method thereof | |
| CN105418834B (en) | Paper-plastic water-based adhesive and preparation method thereof | |
| CN103360536B (en) | Add the Production of PVC method that chainextender coordinates later stage heating process | |
| CN1711860A (en) | Food coating composition comprising protective colloid-stabilized polyacrylate dispersions, use thereof and coated foods produced therewith | |
| CN102070741A (en) | Novel hot-seal adhesive emulsion and preparation method thereof | |
| CN103102851A (en) | Multifunctional water-based vacuum aluminizer composite adhesive and preparation method thereof | |
| CN103951790B (en) | Acetate emulsion and preparation technology thereof | |
| CN107602752B (en) | A kind of copolymerization REPVDC alloy solid resin and its preparation method and application | |
| CN106543298B (en) | A method of addition assistant for emulsifying agent prepares EVA lotion | |
| CN107602753B (en) | A kind of rare earth/metallic compound function monomer and its preparation method and application | |
| CN103059193B (en) | Special PVDC latex coating of cigarette film and its preparation method and application | |
| CN103059202A (en) | Polyvinylidene chloride copolymer emulsion for pharmaceutical packing coating and preparation method and application thereof | |
| CN103059196B (en) | Polyvinyl dichloride (PVDC) latex for ultrahigh-resistance diaphragm used for food packaging and preparation method thereof and application thereof | |
| CN103275263A (en) | Method for preparing ultra-high blocking latex for food packaging | |
| CN108368188B (en) | Multistage aqueous emulsion polymer and aqueous coating composition formed therefrom | |
| EP3385350A1 (en) | Aqueous dispersions with high stability for adhesives and sealants | |
| CN103923581A (en) | Modified white latex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210714 Address after: No. 1919, panchuan Road, Baoshan District, Shanghai, 200949 Patentee after: ANTAINENG (SHANGHAI) HIGH-MOLECULAR MATERIAL Co.,Ltd. Address before: 1919 panchuan Road, Baoshan District, Shanghai, 201900 Patentee before: SHANGHAI LUFENG PROMOTER Co.,Ltd. |